The reactive P-N bond in 1-phospha-2-azanorbornenes is readily cleaved by simple alcohols to afford P-chiral 2,3-dihydrophosphole derivatives as a racemic mixture. The isolation of the products was not possible due to the reversibility of the reaction, which could, however, be stopped by sulfurization of the phosphorus atom, thus efficiently blocking the lone pair of electrons, as exemplified for 6b yielding structurally characterized 8b. Additionally, the influence of the substituent in the α position to the phosphorus atom (H, Ph, 2-py, CN) on the reversibility of the reaction was studied. Extensive theoretical calculations for understanding the ring-closing mechanism suggested that a multi-step reaction with one or more intermediates was most probable.
